EP3453696B1 - Method for producing conjugated diene - Google Patents

Method for producing conjugated diene Download PDF

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Publication number
EP3453696B1
EP3453696B1 EP17792727.4A EP17792727A EP3453696B1 EP 3453696 B1 EP3453696 B1 EP 3453696B1 EP 17792727 A EP17792727 A EP 17792727A EP 3453696 B1 EP3453696 B1 EP 3453696B1
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EP
European Patent Office
Prior art keywords
sulfated
production method
conjugated diene
acid catalyst
solid acid
Prior art date
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Application number
EP17792727.4A
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German (de)
English (en)
French (fr)
Other versions
EP3453696A1 (en
EP3453696A4 (en
Inventor
Takahiro Suzuki
Kosuke SENDA
Yutaka Suzuki
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Kuraray Co Ltd
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Kuraray Co Ltd
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Publication of EP3453696A4 publication Critical patent/EP3453696A4/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/12—Alkadienes
    • C07C11/173—Alkadienes with five carbon atoms
    • C07C11/18—Isoprene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
    • C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-

Definitions

  • the present invention relates to a method for producing a conjugated diene.
  • the present invention relates to a method for producing a conjugated diene through dehydration of a ⁇ , ⁇ -unsaturated alcohol.
  • PTL 3 discloses a method in which isoprene monool or the like is allowed to react in a liquid phase under pressure at a reaction temperature of 100 to 180°C in the presence of a homogenous acid catalyst.
  • a treatment of the acid waste fluid is needed from the viewpoint of environmental protection, so that the process becomes complicated.
  • PTL 4 describes a method of obtaining isoprene through dehydration of 3-methyl-3-buten-1-ol in the presence of a molybdenum catalyst.
  • PTL 5 describes a method of obtaining isoprene through reacting an isobutylene source material with a formaldehyde source material in a liquid-phase one stage reaction.
  • a problem of the present invention is to provide a method capable of producing a conjugated diene in a good yield under mild conditions through dehydration of a ⁇ , ⁇ -unsaturated alcohol.
  • a conjugated diene can be produced in a good yield under mild conditions through dehydration of a ⁇ , ⁇ -unsaturated alcohol.
  • the ⁇ , ⁇ -unsaturated alcohol serving as a raw material in the production method of the present invention is preferably one represented by the following general formula (I) (hereinafter referred to as " ⁇ , ⁇ -unsaturated alcohol (I)").
  • R 1 , R 2 , and R 3 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 1 and R 3 may be connected to each other to form a ring.
  • R 1 , R 2 , and R 3 are those defined above.
  • Examples of the alkyl group having 1 to 10 carbon atoms, which R 1 , R 2 , and R 3 each independently represent, include a methyl group, an ethyl group, various propyl groups (the wording "various" means that all of a linear group and a branched group are included; hereinafter the same), various butyl groups, various hexyl groups, various octyl groups, and various decyl groups. Above all, an alkyl group having 1 to 5 carbon atoms is preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is still more preferred.
  • rings having 5 to 10 carbon atoms such as a cyclopentene ring, a cyclohexene ring, and a cyclooctene ring, are preferred, and a cyclohexene ring is more preferred.
  • R 1 , R 2 , and R 3 it is preferred that at least one of R 1 and R 2 is a hydrogen atom, and R 3 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; and it is more preferred that all of R 1 and R 2 are a hydrogen atom, and R 3 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • Preferred alkyl groups are those mentioned above.
  • ⁇ , ⁇ -unsaturated alcohol (I) examples include those mentioned below.
  • the solid acid catalyst which is used for the production method of the present invention has a Hammett acidity function (H 0 ) of -12.2 or less.
  • H 0 Hammett acidity function
  • B base type
  • BH + an acid type
  • H 0 pK a + log B / BH +
  • the Hammett acidity function is defined according to the following equation while designating a Lewis acid site as "A".
  • H 0 pK a + log B / AB
  • the value of H 0 can be, for example, determined by the amine titration method or the like.
  • the acid catalyst having a Hammett acidity function (H 0 ) of -12.2 or less by using the acid catalyst having a Hammett acidity function (H 0 ) of -12.2 or less, the reactivity is improved, and the conjugated diene can be produced in a high yield.
  • the solid catalyst by using the solid catalyst, not only corrosion of an apparatus and so on and generation of an acidic waste fluid can be suppressed, but also it becomes easy to perform separation and recovery/regeneration/reuse of the catalyst from the reaction system.
  • the solid acid catalyst having a Hammett acidity function (H 0 ) of -12.2 or less is preferably an oxoacid-supported metal oxide.
  • a BET specific surface area as the nitrogen adsorption specific surface area as measured in conformity with the "Determination of the specific surface area of powders (solids) by gas adsorption" described in JIS Z8830:2001 is preferably 20 to 800 m 2 /g, more preferably 25 to 600 m 2 /g, and still more preferably 50 to 500 m 2 /g.
  • the BET specific surface area falls within the aforementioned range, a satisfactory catalytic activity is obtained, and a selectivity of the conjugated diene is improved.
  • the solid acid catalyst may be used after performing aging. By using the aged solid acid catalyst, a high catalytic activity can be exhibited.
  • An aging time is typically 0.5 to 5 hours, and preferably 1 to 3 hours.
  • an aging temperature is typically 100 to 300°C, and preferably 130 to 150°C. In the case where the temperature is too low, drying of the catalyst is liable to be not sufficiently achieved. In addition, in the case where the temperature is too high, there is a possibility that an unpredicted change in catalyst structure is generated, and such is not desired so much.
  • the production method of the present invention can be performed in the absence of a solvent, it is preferably performed in the coexistence of a solvent.
  • a solvent for example, aliphatic hydrocarbons, such as octane, nonane, decane, kerosene, and a liquid paraffin; and aromatic hydrocarbons, such as xylene, toluene, and a high boiling aromatic material are preferred, with aliphatic hydrocarbons being more preferred.
  • a use amount of the solvent in the reaction system is preferably 80 to 99% by mass, more preferably 85 to 97.5% by mass, and still more preferably 90 to 95% by mass.
  • the use amount of the solvent in the reaction system falls within the range of from 80 to 99% by mass, a load to a stirring device is suppressed.
  • the production of high-boiling by-products is suppressed, and not only the selectivity of the conjugated diene can be enhanced, but also the conversion of the ⁇ , ⁇ -unsaturated alcohol can be kept high.
  • An existent amount of the solid acid catalyst in the reaction system is preferably 1 to 20% by mass, more preferably 2.5 to 15% by mass, and still more preferably 5 to 10% by mass. This amount is adjustable by, for example, the use amount of the solvent or the like.
  • the existent amount of the solid acid catalyst in the reaction system falls within the range of from 1 to 20% by mass, the production of high-boiling by-products is suppressed, and not only the selectivity of the conjugated diene can be enhanced, but also the conversion of the ⁇ , ⁇ -unsaturated alcohol can be kept high.
  • a reaction temperature is preferably 100 to 210°C, more preferably 115 to 200°C, and still more preferably 120 to 190°C.
  • the reaction temperature is 100°C or higher, a thoroughly high reaction rate is obtained, and the conjugated diene can be obtained in a high selectivity.
  • the reaction temperature is 210°C or lower, a side reaction of the produced conjugated diene is suppressed, leading to an improvement in yield, and in addition to that, the use amount of a heat source can be suppressed. Thus, such is economically advantageous.
  • a reaction pressure is preferably 0.05 to 2.0 MPa, more preferably 0.075 to 1.5 MPa, and still more preferably 0.09 to 1.0 MPa.
  • the reaction pressure is less than 0.05 MPa, there is a case where it is difficult to obtain a satisfactory reaction temperature.
  • the reaction in a so-called reactive distillation mode in which the solid acid catalyst having an H 0 of -12.2 or less and the solvent are charged, the ⁇ , ⁇ -unsaturated alcohol is continuously fed into a vessel regulated at a predetermined temperature and a predetermined pressure, and the produced conjugated diene and water are continuously distilled out the reaction system.
  • a total amount of the conjugated diene and water distilled out the reactor (a value expressed into a liquid material obtained by cooling after distillation) is preferably 0.8 to 1.2 times, and more preferably 0.9 to 1.1 times of the mass of the ⁇ , ⁇ -unsaturated alcohol to be fed into the reactor per unit time.
  • H 0 -14.6, BET specific surface area: 52.5 m 2 /g.
  • the conversion of 3-methyl-3-buten-1-ol was 88.6%, and the selectivity of isoprene was 67.9%.
  • the selectivity of isobutene as a by-product was 0.8%
  • the selectivity of 1,1-dimethyl-2-propen-1-ol as a by-product was 8.6%
  • the selectivity of ⁇ -methyldihydropyrane as a by-product was 0.5%
  • the selectivity of an isoprene dimer as a by-product was 1.2%.
  • Nafion a registered trademark
  • Example 2 The same operations as in Example 1 were followed, except that the catalyst was changed to 3.1 g of ⁇ -alumina ("E30N4", manufactured by JGC Catalysts and Chemicals Ltd., H 0 ⁇ -5.5, BET specific surface area: 186 m 2 /g). However, the distillation of the reactant was not found, and the production of isoprene was not observed. As a result of analyzing the reaction solution within the reactor, the conversion of 3-methyl-3-buten-1-ol was 23.7%.
  • E30N4 ⁇ -alumina
  • the target conjugated diene could be produced in a high yield under mild conditions.
  • the conjugated diene which is obtained by the production method of the present invention is useful as various chemical products and polymer raw materials, and so on.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
EP17792727.4A 2016-05-06 2017-04-26 Method for producing conjugated diene Active EP3453696B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016092951 2016-05-06
PCT/JP2017/016567 WO2017191794A1 (ja) 2016-05-06 2017-04-26 共役ジエンの製造方法

Publications (3)

Publication Number Publication Date
EP3453696A1 EP3453696A1 (en) 2019-03-13
EP3453696A4 EP3453696A4 (en) 2020-01-08
EP3453696B1 true EP3453696B1 (en) 2021-03-17

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EP17792727.4A Active EP3453696B1 (en) 2016-05-06 2017-04-26 Method for producing conjugated diene

Country Status (8)

Country Link
US (1) US11319261B2 (ru)
EP (1) EP3453696B1 (ru)
JP (1) JP6892187B2 (ru)
KR (1) KR102338451B1 (ru)
CN (1) CN109071379A (ru)
RU (1) RU2734778C2 (ru)
TW (1) TW201806913A (ru)
WO (1) WO2017191794A1 (ru)

Family Cites Families (23)

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Publication number Priority date Publication date Assignee Title
DE1928632A1 (de) 1969-06-06 1970-12-10 Basf Ag Verfahren zur Herstellung von Isopren
DE2031900C3 (de) * 1970-06-27 1979-02-01 Basf Ag, 6700 Ludwigshafen Verfahren zur Herstellung von Isopren
JPS5242763B2 (ru) 1971-01-12 1977-10-26
JPS471571A (ru) 1971-06-25 1972-01-26
US3809727A (en) * 1972-04-24 1974-05-07 Phillips Petroleum Co Dehydration of 3-methyl-3-buten-1-ol
JPS5236725B2 (ru) 1973-05-07 1977-09-17
JPS5236603A (en) * 1975-09-16 1977-03-22 Kuraray Co Ltd Process for preparation of isoprene
US4053536A (en) * 1976-05-25 1977-10-11 Phillips Petroleum Company Dehydration of olefinically unsaturated alcohols
JPS596181B2 (ja) * 1979-08-27 1984-02-09 日本鉱業株式会社 固体酸触媒
JPS57130928A (en) * 1981-02-06 1982-08-13 Nippon Zeon Co Ltd Synthetic method of isoprene
US4668832A (en) * 1985-10-08 1987-05-26 The Dow Chemical Company Dehydration of halogenated, unsaturated alcohols to form halogenated, conjugated dienes
JPH02500363A (ja) * 1986-10-01 1990-02-08 ネルソン　リサーチ　アンド　デベロプメント　カンパニー 酸を触媒とする方法
JP2566814B2 (ja) 1988-05-13 1996-12-25 株式会社ジャパンエナジー 炭化水素転化用固体酸触媒及びその製造方法
JPH05293375A (ja) 1992-04-17 1993-11-09 Japan Energy Corp 固体超強酸触媒及びその製法
RU2116286C1 (ru) * 1997-07-21 1998-07-27 Синицын Александр Васильевич Способ получения изопрена
US6448198B1 (en) * 1997-10-13 2002-09-10 Total Raffinage Distribution S.A. Acid catalyst with a sulfated zirconia base and its uses
FR2769519B1 (fr) * 1997-10-13 1999-12-31 Total Raffinage Distribution Catalyseur acide a base de zircone sulfatee et ses utilisations
RU2368593C1 (ru) * 2008-05-13 2009-09-27 Открытое акционерное общество "Нижнекамскнефтехим" Способ выделения изобутилена
ZA201102109B (en) * 2008-09-15 2013-10-30 Goodyear Tire & Rubber Conversion of prenyl derivatives to isoprene
JP5798871B2 (ja) 2011-09-30 2015-10-21 株式会社クラレ イソプレンの製造方法
JP2013213028A (ja) * 2012-03-07 2013-10-17 Mitsubishi Chemicals Corp 共役ジエンの製造方法
SG11201709802XA (en) * 2015-06-03 2017-12-28 Kuraray Co Method for producing conjugated diene
CN105152832A (zh) * 2015-10-13 2015-12-16 宁波金海晨光化学股份有限公司 一种合成异戊二烯的工艺方法

Non-Patent Citations (1)

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Also Published As

Publication number Publication date
US11319261B2 (en) 2022-05-03
EP3453696A1 (en) 2019-03-13
RU2018138691A3 (ru) 2020-06-08
US20190135714A1 (en) 2019-05-09
KR102338451B1 (ko) 2021-12-10
CN109071379A (zh) 2018-12-21
EP3453696A4 (en) 2020-01-08
KR20190004279A (ko) 2019-01-11
TW201806913A (zh) 2018-03-01
JPWO2017191794A1 (ja) 2019-03-07
WO2017191794A1 (ja) 2017-11-09
JP6892187B2 (ja) 2021-06-23
RU2018138691A (ru) 2020-06-08
RU2734778C2 (ru) 2020-10-23

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